ORGANIC CHEMISTRY –II 2. ALCOHOLS ETHERS AND PHENOLS

•

ALCOHOLS : Alcohols are the organic compounds with – OH group as the functional group. They are monoalkyl derivatives of water. Based on the number of OH groups alcohols are classified as 1) Monohydric 2) Dihydric 3) Trihydric 4) Polyhydric Monohydric alcohols → one – OH group Eg: CH3 – OH , C2H5 – OH Dihydric alcohols → two – OH groups (glycols)

CH2 − CH2 | | OH OH

→ ethylene glycol

CH2 – CH(OH)2

→ ethyledene glycol → propylene glycol

CH3 − CH− CH2 | | OH OH

CH3– CH2 – CH (OH)2 → n propyledene glycol OH | CH3 − C − CH3 | OH

•

→ isopropyledene glycol

Based on the carbon to which OH group is attached alcohols are of 3 types. 1) primary alcohols 2) Secondary alcohols of 3) Tertiary alcohols Primary alcohols: CH3 – CH2 – OH

CH3 − CH − CH2 − OH | CH3

CH3 – CH2 – CH2 – OH CH3 | CH3 − C − CH2 − OH | CH3

(Ethyl alcohol)

(Propylalcohol)

(Iso butyl alcohol)

Secondary alcohols : CH3 − CH− CH3 | OH

(Isopropyl alcohol)

(neo-pentyl alcohol)

Tertiary alcohols : CH3 − CH2 − CH− CH3 | OH

CH3 | CH3 − C − OH | CH3

CH3 | C2H5 − C − OH | CH3

(sec butylalcohol) (tertiary butyl alcohol) (tertiary amyl alcohol)

1

Organic Chemistry – II •

Isomerism in alcohols : They exhibit chain, position, functional isomerism. For saturated monohydric alcohols → CnH2n+2O (or) Cn H2n+1OH functional isomers are C2H 6O → H3C – CH2 – OH (ethyl alcohol) H3C – O – CH3 (dimethyl ether) positional isomers are C2H6O2→ CH3 – CH (OH)2 ( ethyledene glycol) CH2 − CH2 ( ethyleneglycol ) | OH

C3H8O →

| OH

CH3 – CH2 – CH2 – OH

( n – propyl alcohol) (isopropyl alcohol)

CH3 − CH− CH3 | OH

C4H10O →

CH3 – O - C2H5 a) CH3 – CH2 – CH2 – CH2 – OH b) CH3 − CH2 − CH− CH3

(methyl ethyl ether) (n – butyl alcohol) (sec butyl alcohol)

c)

(isobutyl alcohol)

| OH CH3 − CH − CH2 − OH | CH3

CH3 – CH2 – O – CH2 – CH3 CH3 – O – CH2 – CH2 – CH3

(diethyl ether) (methyl propyl ether)

CH3 | d) CH3 − C − OH | CH3

(tertiary butyl alcohol)

CH3 − O − CH − CH3 | CH3

• • •

(isopropyl methyl ether )

a, b → position ; a, c → chain a, d→position and chain b, c → position and chain b, d → chain c, d → position If tetrahedral carbon is bonded to four different atoms or different groups of atoms it is called asymmetric carbon. Organic compound containing one or more asymmetric carbons will exhibit optical isomerism. Certain alcohols having asymmetric carbon will exhibit optical isomerism. CH3 – OH CH3 – CH2 – OH OH CH3 – CH2 – CH2 – Doesn’t show optical isomerism CH3 − CH − OH | CH 3

2

Organic Chemistry – II CH3 − CH− CH2 − CH3 | OH CH3 − CH− COOH | OH

• •

Exhibits optical isomerism

Ethyl alcohol : Grain alcohol or spirit of wines ( C2H5OH) Preparation : By the hydrolysis of ethyl halide : (industrial method) Ethyl halide on hydrolysis with aqueous sodium hydroxide or potassium hydroxide gives ethyl alcohol. C 2H5 X + NaOH → CH3 CH2 OH + NaX ; X = Cl, Br, I In the place of NaOH or KOH, AgOH can be used.

•

By the hydrolysis of ester : Hydrolysis of ethyl acetate with aqueous alkali gives ethyl alcohol. CH 3 COOC 2 H 5 + KOH (aq ) → CH 3 COOK + C 2 H 5 OH

•

By the hydration of Ethylene :(industrial method ) Ethylene on reaction with conc. sulphuric acid at 75–80°C gives ethylalcohol. CH2 = CH2 + H − HSO4 → CH3 − CH2 − HSO4 CH3 − CH2 − HSO4 + H − OH → CH3 − CH2 − OH + H2SO4

•

By the reduction of Acetaldehdye (CH3–CHO) : Acetaldehyde on reduction with Hydrogen and Nickel or Lithium aluminum hydride gives ethyl alcohol. H2 / Ni or CH 3 − CHO + H 2 ⎯⎯ ⎯ ⎯→ CH 3 − CH 2 − OH LiAlH4

•

From Grignard reagent and formaldehyde: Methyl magnesium halide on reaction with formaldehyde followed by hydrolysis gives ethyl alcohol. δ+

δ−

δ−

δ+

H−OH H2 C = O+ CH3 − MgBr → CH3 − CH2 − OMgBr ⎯⎯ ⎯ ⎯→ CH3 − CH2 OH + Mg(OH)Br

•

• •

Formaldehyde+any grignard reagent→ primary alcohol Fermentation of molasses : The breaking of complex organic molecule into smaller ones in the presence of enzymes is called fermentation. In any fermentation process the by product is CO2. Molasses is a dark, brown coloured liquor left after the crystallization of sugar. Molasses still contain about 40% sugar. It is diluted to 10% sugar and yeast cells are added. PH is maintained at 4 by adding dilute H2SO4. Temperature is maintained between 300C and 400C. Ammonium Sulphate or Ammonium phosphate is added to yeast cells which acts as food for yeast. Yeast cells produce invertase and zymase enzyme In presence of invertase enzyme sucrose (sugar) is hydrolysed to glucose and fructose Invertase C12H22 O11 + H2 O ⎯⎯ ⎯⎯ ⎯→ C 6H12 O 6 + C 6H12 O 6 sucrose (Glu cos e ) (Fructose)

•

Glucose or fructose is then converted into alcohol in presence of zymase enzyme. zymase

C 6H12 O 6 ⎯⎯ ⎯ ⎯→ 2C 2H5 OH + 2CO 2

•

The alcohol obtained above is 6 – 10% pure which is called as wash or wort. Wash is further concentrated to the 95.6% by fractional distillation. 95.6% alcohol is called rectified spirit. 95.6 % alcohol and 4.4% water will form constant boiling mixture [azeotropic mixture] therefore it can’t be further concentrated to 100% alcohol by normal distillation methods. Quicklime (CaO) or magnesium ethoxide [Mg(OC2H5)2] can be used to convert 95.6% into 100% 3

Organic Chemistry – II • •

•

alcohol which is called absolute alcohol or absolute spirit. Anhydrous CaCl2 is laboratory desiccant but CaCl2 should not used for drying alcohol as if forms an addition compound with it. That addition compound is CaCl2.3C2H5OH. Fermentation of starch : Starch is present in wheat, maize, potato etc. The source of starch is crushed and treated with steam and the product is called Mash. The product is added to germinated Barley seeds which is called malt. Malt contains diastase enzyme. In presence of diastase enzyme starch is hydrolyzed to give maltose diastase 2(C 6H10 O 5 )n + nH 2 O ⎯⎯ ⎯⎯→ nC12H22 O11 (maltose ) (starch )

Yeast cells are added to produce maltase and zymase enzymes. In presence of maltase, maltose, converts into glucose which then converts into ethyl alcohol in the presence of zymase enzyme. maltose

C12H22O11 + H2O ⎯⎯ ⎯ ⎯→ 2C6H12O 6

(glu cos e )

zymase

C 6H12 O 6 ⎯⎯ ⎯ ⎯→ 2C 2H5 − OH + 2CO 2 ↑

The ethyl alcohol obtained is 6 – 10%. It is further concentrated to 100% alcohol as listed above. Physical properties : 1) It is a colourless liquid with characteristic smell. 2) It has burning taste 3) It forms hydrogen bonds with water and also with it itself therefore it exists as associated liquid, soluble in water and boiling point is very high (78.1 0C). 4) It’s dissolution in H2O is exothermic and there is slight contraction in volume. 5) Non ideal solution. • • •

Chemical reactions: The reactions of alcohols involve either cleavage of O – H bond or C – OH bond. Reactivity of alcohols involved in cleavage of O – H R −O−H

Primary alcohol>secondary alcohol>tertiary alcohol • Reactivity of alcohols which involve cleavage of C–OH R −O−H

Primary alcohol C 2H5 − OH > CH ≡ CH > CH2 = CH2 > CH3 − CH3

primary alcohol>secondary alcohol>tertiary alcohol 2) with grignard reagent : Ethyl alcohol on reaction with Grignard reagent forms alkane. C 2H5 OH + CH3 − MgBr → CH4 + C 2H5 OMgBr

4

Organic Chemistry – II 3) with acetic acid (esterification) : Ethyl alcohol on reaction with carboxylic acid gives ester. This reaction is catalysed by mineral acid. H 3O + C 2H5 OH + CH3 COOH CH3 COOC 2H5 + H − OH This reaction is called Fischer esterification 4) With acetyl chloride and acetic anhydride : With acetyl chloride and acetic anhydride also ethyl alcohol gives ester. C 2H5 OH + CH3 COCl → CH3 COOC 2H5 + HCl

C 2H5 OH + (CH 3 CO )2 O → CH 3 COOH + CH 3 COOC 2H5

5) With hydrogen halides : Ethyl alcohol on reaction with hydrogen halides in the presence of anhydrous ZnCl2 gives ethyl halide. an hydrous C 2H5 OH + HCl ⎯⎯ ⎯ ⎯⎯→ C 2H5 − Cl + H2O ZnCl2

C 2H5 OH + HBr → C 2H5Br + H2 O

6) With phosphorous halides : Ethyl alcohol on reaction with phosphorus halides gives ethyl halides. 3 C 2H5 OH + PCl3 → 3C 2H5 Cl + H3PO 3 3 C 2H 5 OH + PBr3 ⎯⎯→ 3C 2H 5 Br + H 3 PO 3 3 C 2 H 5 OH + PI 3 ⎯⎯→ 3C 2H 5I + H 3 PO 3 C2H5 − OH + PCl5 → C2H5Cl + POCl3 + HCl

8) With SOCl2 : Thionyl chloride reacts with ethyl alcohol to give ethyl chloride. C 2H5 OH + SOCl 2 → C 2H5 Cl + SO 2 + HCl

9) Dehydration : Ethyl alcohol on dehydration gives different products at different temperatures. con.H SO

2 4 C 2H5 OH ⎯⎯⎯⎯ ⎯⎯ → C 2H5 − HSO 4 + H2O

110 0 C

(ethylhydrogen sulphate) conc.H 2 SO 4

2C 2H5 OH ⎯⎯⎯⎯⎯⎯ ⎯→ C 2H5 − O − C 2H5 + H2O 0 140 C

(diethyl ether) conc.H2 SO 4

C 2H5 OH ⎯⎯⎯⎯⎯⎯ ⎯→ C 2H4 + H2 O 0 170 C

•

(ethylene) In presence of excess of H2SO4 product is C2H4 with excess of alcohol the product is diethyl ether. Instead of conc. H2SO4, Alumina can be used. conc.Al O

3 2C 2H5 OH ⎯⎯⎯⎯2⎯⎯ → C 2H5 − O − C 2H5 + H2O

250 0 C conc.Al 2 O 3

C 2H5 OH ⎯⎯⎯⎯⎯⎯→ C 2H 4 + H2O 350 0 C

10) Reduction : Ethyl alcohl is reduced to ethane by HI / red P. red P

C 2H5 OH + 2HI ⎯⎯ ⎯⎯→ C 2H6 + I2 + H 2 O

11) Dehydrogenation (oxidation): a) Ethyl alcohol in the presence of copper at 300°C gives acetaldehyde. 0

Cu,300 C CH3 − CH2 − OH ⎯⎯ ⎯⎯ ⎯→ CH3 − CHO + H2

(acetaldehyde)

5

Organic Chemistry – II b) On oxidation with acidified potassium permanganate (KMnO4) or potassium dichromate (K2Cr2O7) ethyl alcohol forms acetic acid. [O]

4 CH3 − CH2 − OH + [O] ⎯⎯⎯⎯ ⎯→ CH3 − CHO ⎯⎯ ⎯→ CH3 − COOH

KMnO or K 2Cr2O7

pri aldehyde .

12) with Chlorine : Chlorine oxidises ethyl alcohol to chloral. CH3 − CH2 − OH + 3Cl2 → CCl3 − CHO + 3HCl chloral

13) with bleaching powder : Ethyl alcohol and bleaching powder mixture on distillation gives chloroform. C 2H5 OH + CaOCl2 + H2O → CHCl3 + (HCOO)2 Ca + HCl

14) Iodoform reaction : Yellows crystals of CHI3 will be formed when ethylalcohol is treated with I2 solution and potassium hydroxide. C 2H5 OH + 4I 2 + 6KOH → CHI3 ↓ + 5KI + HCOOK + 5H 2 O

•

Alcohols containing CH3 − CH− or Aldehydes or ketones containing CH3 − C − will react with || O

| OH

iodine and alkali to give iodoform which is yellow crystalline solid. ETHERS : [R – O – R1 →alkoxy alkanes] •

ether is the dialkyl derivative of water

•

ether is the anhydride of alcohol. Naming of ethers CH3 – O – CH3 CH3 – O – C2H5 C2H5 – O – C2H5 CH3 – O – CH2 – CH2 – CH3 CH3 − O − CH

C 2H5 − O − CH − CH2 − CH3 | CH3

•

IUPAC

Common name

Methoxy methane methoxy ethane Ethoxy ethane 1 – methoxy propane

Dimethyl ether ethyl methyl ether Diethyl ether Methyl – n – propy ether

2 – methoxy propane

Methyl isopropyl ether

2 – ethoxy butane

Ethyl secondary butyl ether

CH 3 CH 3

•

⎡H − O − H ⎤ ⎢ ⎥ ⎣R − O − R⎦

Ethers are classified into two types based on the nature of alkyl groups. 1) Symmetrical ethers (or) simple ethers are R = R′ R – O – R CH3 – O – CH3 C2H5 – O – C2H5 2) unsymmetrical ethers (or) mixed ethers : R ≠ R′ R – O – R′ CH3– O – C2H5 C2H5 – O – CH2 – CH2 – CH3 Isomerism shown by ethers: Ethers will exhibit metamerism, functional isomerism and chain isomerism. 6

Organic Chemistry – II CH3 − O − CH3 C 2H5 − OH

Functional isomers

C2H5 − O − C2H5 CH3 − O − CH2 − CH2 − CH3 CH3 − O − CH − CH3 | CH 3

•

Metamers

General molecular formula of ether → CnH2n+2O Diethyl ether (sulphuric ether) : Preparation : 1) Dehydration : a) By the dehydration of ethyl alcohol in the presence of conc. H2SO4 at 1400C. conc.H2SO4 2C 2H5 OH ⎯⎯ ⎯⎯ ⎯ ⎯→ C 2H5 − O − C 2H5 + H2 O 0 140 C

b) By the dehydration of ethyl alcohol in presence of anhydrous alumina at 2500C. Al2O3 2C 2H5 OH ⎯⎯ ⎯ ⎯→ C 2H5 − O − C 2H5 + H2 O 0 250 C

2) From ethyl chloride : By the reaction of ethyl chloride with dry silver oxide. 2C 2H5 Cl + Ag 2 O → C 2H5 − O − C 2H5 + 2AgCl

3) Williamson’s synthesis : Alkyl halides react with sodium alkoxides to produce ethers. This method is suitable for the preparation of both simple and mixed ethers. C 2H5 Cl + NaOC 2H5 → C 2H5 − O − C 2H5 + NaCl

•

Physical properties : 1) It is a colourless liquid with pleasant smell. 2) It does not form hydrogen bonds and will not exist as associated liquid. Therefore it is highly volatile, low boiling point 307.50C and it is slightly miscible with water. 3) It is inflammable. 4) It’s vapours cause unconsciousness. 5) It forms explosive mixture with air [ether +O2 → etherperoxide] O 110 C2H 0 C2H

• • • •

In ether ‘O’ is sp3 hybridised, shape is angular. Bond angle is 1100 due to the repulsions between bond pair and because of bulky nature of alkyl groups. It is slightly polar and its μ ≠ 0. Chemical reactions: Ethers are chemically inert because ‘O’ is flanked in between two bulky alkyl groups. Therefore ethers are not easily oxidisable and they will not decolourise permanganate or dichromate. 1) α - halogenation : The α - hydrogens present in ether are substituted by halogen atoms. α

dark

α1

CH3 − CH 2 − O − CH 2 − CH 3 + 2Cl 2 ⎯⎯ ⎯→ CH3 − CH− O − C H− CH3 + 2HCl (α, α1 −dichloro diethyl ether)

7

|

|

Cl

Cl

Organic Chemistry – II Cl Cl | | CH3 − CH2 − O − CH2 − CH3 + 2Cl 2 ⎯⎯ ⎯⎯→ CH3 − C − O − C − CH3 (αα, α1 α1 −tetrachloro diethyl ether) | | Cl Cl sunlight

In dark the two α - hydrogens are substituted by two chlorines on reaction with chlorine. 2) with air : Diethyl ether when exposed to air forms a mixture due to the formation of diethyl peroxide. C 2H 5 − O − C 2H 5 +

1 O 2 → C 2H 5 − O − O − C 2H 5 (explosive ) 2

(or)

C 2 H 5 − O− C 2 H 5

↓ O

It is

freed from peroxide by treating with ferrous sulphate. 3) with dil.H2SO4 : Diethyl ether is hydrolysed to ethyl alcohol in presence of sulphuric acid dil.H SO

4 C 2 H 5 − O − C 2 H 5 + H − OH ⎯⎯ ⎯2⎯ ⎯ → 2C 2 H 5 OH

4) with cold and conc. mineral acids. Ether reacts with cold and conc. mineral acids like HCl, H2SO4, HNO3 etc. to form oxonium salts. Formation of these oxonium salts with the mineral acids is the indication of its basic nature. ••

(C 2H5 )2 O+ HCl → (C 2H5 )2 OH+ Cl−

(diethyl oxonium chloride)

••

(C 2H5 )2 O+ H2SO 4 → [(C 2H5 )2 OH •• ••

]

+ −2 2 SO 4

(diethyl oxonium sulphate )

5) with HI: With cold HI, one C – O bond is cleaved and the products are ethyl alcohol and ethyl iodide. C 2H5 − O − C 2H5 + HI → C 2H5 − OH + C2H5 − I •

With hot and excess of HI , both C – O bonds are cleaved and two moles of C2H5 – I are formed C 2H5 − O − C 2H5 + 2HI → 2C 2H5 − I + H2O

• • •

In case of mixed ethers I– of HI is added to smaller alkyl group. CH3 − O − C 2H5 + H I → CH3 – I + C2H5 – OH Ziesel’s method is useful to detect and estimate the number of methoxy groups present in the given ether. The reaction of ether with HI forms the basis for Ziesel’s method. 6) with PCl5 : with PCl5 diethyl ether gives ethylchloride Δ C 2H5 − O − C 2H5 + PCl5 ⎯⎯→ 2C 2H5 Cl + POCl3

7) Dehydation : on dehydration in the presence of alumina diethyl ether gives ethylene. an.Al2CO3 C2H5 − O − C2H5 ⎯⎯ ⎯0⎯ ⎯→ 2C 2H4 + H2O 360 C

8) with CO: In the presence of BF3 at 150°C and 500 atm pressure diethyl ether reacts with CO and forms ethyl propionate (Ester) BF ,150 0 C

C2H5 − O − C2H5 + CO ⎯⎯3⎯ ⎯⎯→ C2H5 − COOC2H5 (ethyl propionate) 500 atm

9) Reduction : Diethyl ether reduces to ethane on reduction with Na/liq.NH3. Na / liq.NH3 C 2H5 − O − C 2H5 + 2H ⎯⎯ ⎯ ⎯⎯→ C 2H6 + C 2H5 OH

8

Organic Chemistry – II ELECTROPHILIC SUBSTITUTION. 1) HALOGENATION:

2) NITRATION:

3) FRIEDEL-CRAFTS REACTION:

9

Organic Chemistry – II USES : ETHER IS USED IN/AS 1. a solvent for oils, fats, waxes, plastics etc. 2. the extraction of organic compounds from aqueous solutions. 3. an inert medium for various reactions (ex.Wurtz reaction) and preparation of RMgX 4. an anaesthesia in surgery without causing any damage to heart or lungs. (Recently, HALOTHANE is widely used for this purpose since it is harmless and quick in action CF3CHClBr. ) (IUPAC name : 2-Bromo-2- chloro-1,1,1-trifluroethane) 5. NATALITE(mixture of Alcohol and Ether), a substitute for petrol 6. Refrigerant along with dry ice (solid CO2 ) which produces a temperature around -110°C i) Enthrane (CHFCl − CF2 − O − CHF2 ) and isoflurane ( CF3CHCl − O − CHF2 ) are used as anesthetics in place of diethyl ether as the later one has slow effect. Substituted anisols are used as flavourings and in perfumes due to their pleasant odour. ii) Eg :

1.ANITHOLE is a constituent of anise seed.

2.EQUGINOL is present in cloves.

3.VANILLIN is present in oil of vanilla been

4.THYMOL is present in thyme and mint are used as flavourings and in perfumes.

10

Organic Chemistry – II

Identification of primary , secondary , tertiary alcohols Test Primary alcohol Secondary alcohol Tertiary alcohol 1) Lucas test : No reaction Reacts with in Reacts within The alcohol is (No turbidity) 5 minutes to 30 seconds to give treated with Lucas give turbidity turbidity reagent 2) Victor Meyer’s : test : The alcohol

Red colouration is observed

Blue colouration is observed

No colour is produced

is treated with red

RCH 2OH ↓ I 2 / red P

R2CHOH ↓ I 2 + red

↓ I 2 + red P

RCH 2 I ↓ AgNO2

R2CHI ↓ AgNO2

↓ AgNO2 R3CNO2

RCH 2 NO2 ↓ HNO2

R2CHNO2 ↓ HNO2

↓ HNO2 & alkali

and finally made

(Nitrolic acid)

(pseudo nitrol)

alkaline

↓ alkali

phosphorous and and the product is treated with and then with nitrous acid

R3COH

P

R3CI

No reaction.

( NaNO2 + H 2 SO4 )

red colouration 3) Catalytic

Aldehyde, H2 is

dehydrogenation

produced

with copper at

3000 c

↓ alkali blue colouration

RCH 2OH ↓

Ketone, H2 is produced

R2COH →

Dehydration takes place

giving alkene and H2O

R2CO + H 2

(CH 3 )3 COH

→

CH 3 − C = CH 2 + H 2O 1

RCHO + H 2

CH 3

4) Oxidation

(O ) RCH 2OH ⎯⎯→

(O ) R2CHOH ⎯⎯→

with acidified

RCHO

R2CO

Ketone + acid ⎯⎯→

↓ (O) RCOOH

↓ (O)

Mixture of acids

KMnO4

same number of carbon atoms in alcohol, aldehyde and acid

Mixture of alcohol and ketone contain same no. of carbons but acids contains lesser no. of carbons

11

R3 C − OH

(O) ⎯⎯→ (O )

ketone contains lesser no. of carbons than . alcohol. Acid contain still lesser no. of carbons than that of ketone.

Organic Chemistry – II MECHANISM OF DEHYDRATION : It takes place in three steps : i) CH 3 − CH 3 − OH + H 2 SO4 ⇔ ..

CH 3 − CH 2 − + O| − H + OSO3 H H ii) Formation of carbonation. It is the slowest step or rate determining step. ..

+

..

CH 3 − CH 2 − + O| − H ⇔ CH 3 − C H 2 + H 2 O : H iii) Elimination of proton to get alkene

Since the rate determining step is the formation of carbocation, the rate of dehydration is directly proportional to the formation of carbocation. Since the stability of carbocation is 30 > 20 > 10 , the order of dehydration of alcohols is ( CH 3 )3 COH > ( CH 3 )2 CHOH > CH 3 − CH 2OH Dehydration of alcohol requires 95% H 2 SO4 at H 2 SO41700 C , 20 alcohol requires 75% H 2 SO4 at 1000, where 30 as alcohol requires 5% H SO at 500 C . 2

•

•

4

The dehydration of 1o alcohol goes by E2 mech nism, but that of 2o and 3o alcohols go by E1 mechanism. When more than one product is formed, the major product is according to Zaitsev’s rule. It states that hydrogen is removed from β − carbon that is bonded to the least number of hydrogen atoms.( β -elimination) Eg. Dehydration of 2-butanol predominantly gives 2-butene. Conc CH 3 − CH 2 − CHOH − CH 3 ⎯⎯⎯ → H 2 SO4

CH 3 − CH = CH − CH 3 + CH 3 − CH 2 − CH = CH 2 2-butene(major) 1-butene (minor) FORMATION OF ADDTION COMPOUNDS : Ethyl alcohol reacts with anhydrous metal salts to form addition compounds (that is alcohol of crystallisation) a) C2 H 5OH .3CaCl2 , C2 H 5OH .6MgCl2 , C2 H 5OH .3CuSO4

USES OF SOME IMPROTANT COMPOUNDS (Methanol and ethanol) METHANOL 1. Methanol a colourless liquid with b.pt 670 C .is used as solvent, paints, varnishes, shellac etc., 2. Used in the manfacture of HCHO, perfumes and dyes. 3. Used in the preparation of methylated spirt, a mixture of recatified spirit (95.6% ethyl alcohol + 4.4%water) and methyl alcohol making ethyl alcohol unfit for drinking . 4. Two types of methylated spirits: a) mineralised spirit = 90% rectified spirit + 9% methyl alcohol + 1% pyridine

12

Organic Chemistry – II 5.

b) Surgical spirit = 95% rectified spirit + 5% MeOH In denaturation of ethyl alcohol copper sulphate is added to give colour and pyridine is added to make it a foul smelling liquid. Because of denaturation alcohol becomes unfit for drinking.

USES OF ETHYL ALCOHOL 1. As a solvent for pharmaceutical preparations, paints, perfumes, varnishes, gums etc., 2. In alcoholic bevarages. 3. As reaction medium, extractant and crystallsing 4. A source for the preparation of acetaldehyde, chloral, chloroform, iodoform, acetic acid ether etc. 5. A preservative for biological specimens, an antifreeze for automobile radiotors, a fuel in spirit lamps, stoves, a petrol substitute known as power alcohol. PERPARATION OF WINE Grapes are the source of sugar and yeast. Sugar increases in ripe grapes and yeast grows on the outer skin. On crushing the grapes, sugar and enzyme come in contact and fermentation starts in anaerobic conditions. If air is present it oxidises alcohol to acids

PHENOL NAMING OF PHENOLS Molecule

Common name

IUPAC name

Phenol

Phenol

O-cresol

m-cresol

p-cresol

Catechol

2-methyl phenol

3-methyl phenol

4-methyl phenol

Benzene-1,2-diol 13

Organic Chemistry – II

Resorcinol

Benzene-1,3-diol

Hydroquinone (or)quinol Benzene-1,4-diol

2,6-dimethyl phenol METHODS OF PREPARATION OF PHENOL : 1) Phenol was first isolated from coaltar. 2) From haloarenes

HCl ⎯⎯ ⎯ →

3)

350 C & 320 atm + NaOH ⎯⎯⎯⎯⎯⎯ → From diazonium salt :

4)

0 −5 C + NaNO2 + HCl ⎯⎯⎯ → From benzene sulphonic acid :

o

o

conc . H 2 SO4 , SO3 ⎯⎯⎯⎯⎯ ⎯ →

5)

H 2O , warm ⎯⎯⎯⎯ →

molten NaOH ⎯⎯⎯⎯⎯ →

HCl ⎯⎯ ⎯ →

From cumene : Phenol is manufactured from cumene (isopropyl benzene)

+

O2 ( oxidation with air ) ⎯⎯⎯⎯⎯⎯⎯ → +CH 3COCH 3 cumene hydroperoxide

H / H 2O ⎯⎯⎯⎯ →

14

+ N 2 + HCl

+ NaCl

Organic Chemistry – II ACIDITY OF PHENOLS : The reactions of phenol with metals as well as NaOH indicate it is relatively more acidic than alcohols and also water. This is explained on the basis of the structure of phenol. The hydroxyl group in phenol is directly attached to sp 2 carbon of benzene ring. The sp 2 carbon attached to ‘O’ being more electronegative than sp 3 carbon of alcohols, it decreases the electron density on oxygen. Because of this oxygen develops still more electron seeking character and releases proton by taking the shared pair of electrons with it. The acidic nature of phenol can also be explained .On the basis of resonance stabilization of phonoxide ion. Electron withdrawing groups of phenol increase the acidic nature. Electron releasing group of phenol decrease the acidity of phenols. Acidic strength increases with the decrease of the P K a values. The order of the strength of phenols is as follows

>

>

>

>

>

>

>

=

PHYSICAL AND CHEMICAL PROPERTIES OF PHENOLS PHYSICAL : 1) Phenol has higher boiling point than the arenes or haloarenes or ethers of same molecular weight. It is due to the formation of intermolecular hydrogen bond. 2) Phenols are relatively more soluble in water due to their ability to form hydrogen bonding with water. 3) As the hydrocarbon part increases in size and mass, the solubility decreases. CHEMICAL PROPERTIES : 1) Acidic nature of phenol : Alcohols and phenols react with active metals like Na, K, Al etc to liberate hydrogen gas. 2 ROH + 2 Na → 2 RONa + H 2 C6 H 5OH + 2 Na → 2C6 H 5ONa + H 2 Phenols also react with aqueous NaOH solution to produce the salt sodium phenoxide and water. C6 H 5OH + NaOH → C6 H 5ONa + H 2O The acidic nature of alcohols is due to the polar nature of O-H group. Electron releasing groups like alkyl groups increase the electron density on oxygen and decrease the polarity of O-H bond. This decreases the acidic strength. The order of acidic strength is H 2O > RCH 2OH > R2CHOH > R3COH 15

Organic Chemistry – II Even through the electron releasing groups like −CH 3 , −C2 H 5 etc decrease the acidic strength of phenol, Phenol does not liberate CO2 with Na2CO3 or NaHCO3 because phenol is weaker acidic than carbonic acid and carboxylic acids. ESTERIFICATION OF PHENOL : Phenols react with carboxylic acids and their derivatives like acid chlorides and anhydrides to form esters. This reaction (benzoylation ) is called Schotten-Baumann reaction. C6 H 5OH + RCOOH → C6 H 5 − O − CO − R + H 2O pyridine C6 H 5OH + RCOCl ⎯⎯⎯→ C6 H 5 − O − CO − R + HCl Salicylic acid on acetylation gives acetyl salicylic acid known as Aspirin.

conc . H 2 SO4 ⎯ → + (CH 3CO) 2 O ⎯⎯⎯⎯

Electrophilic aromatic substitution reactions of phenol In phenol, -OH group is ring activating and ortho and para directing as these positions get more electron density through resonance structures. a) NITRATION :

dil . HNO3 ⎯⎯⎯⎯ → + O-nitrophenol is steam volatile due to intramolecular hydrogen bond. P-nitrophenol is less volatile due intermolecular hydrogen bond. Phenol when treated with conc. HNO3 gives 2,4,6-trinitrophenol known as picric acid

conc . HNO3 ⎯⎯⎯⎯ → Now a days picric acid is prepared by treating phenol with conc. H 2 SO4 and then with conc. HNO3 .

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Organic Chemistry – II

conc . H 2 SO4 ⎯⎯⎯⎯→

conc . HNO3 ⎯⎯⎯⎯ →

b) HALOGENATION :

Br2 in CS2 at 0 C ⎯⎯⎯⎯⎯⎯ → o

+

Here no Lewis acids like are required because highly activating effect of -OH group polarises bromine quickly. Phenol reacts with bromine water and gives 2,4,6-tribromo phenol (white precipitate)

H 2O +3Br2 ⎯⎯⎯ → 0 − 50 C

c) REIMER-TIEMANN REACTION : Phenol when treated with chloroform in the presence of NaOH give salicylaldehyde. Mechanism : i) CHCl + OH ⇔ H O + CCl →: CCl + Cl Dichloro carbene ( : CCl2 ) is the attacking electrophile in this reaction : −

3

ii)

−

2

3

−

2

+ : CCl2 →

→

↓ NaOH

d) KOLBE’S REACTION :

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Organic Chemistry – II

+

NaOH i ) CO2 & ii ) H ⎯⎯⎯ → ⎯⎯⎯⎯⎯⎯ → e) ACTION OF ZINC DUST : Phenol on heating with zinc dust produces benzene. f) OXIDATION : Phenol oxidation with chromic acid ( Na2Cr2O7 + H 2 SO4 ) produces benzoquinone, which is a conjugate diketone.

chromic acid ⎯⎯⎯⎯⎯ → H 2CrO4

g) FRIES REARRANGEMENT :

anhydrous AlCl3 + (CH 3CO) 2 O ⎯⎯⎯⎯⎯ ⎯ →

AlCl3 ⎯⎯⎯⎯⎯ → Re arrangement

+

USES OF PHENOL : 1) It is raw material for the manufacture of important dyes, drugs, pharmaceuticals, polymers and several other compounds. 2) It is strong antiseptic. 2,4-dichloro-3,5 dimethyl phenol is used as powerful antiseptic under the name Dettol. 3) It is used as a preservative for ink. 4) It is used in the manufacture of drugs like Aspirin, Salol etc. 5) It is used for causterising wounds caused by the bite of mad dogs. Tests of Phenol : i) Aqueous solution of phenol gives violet colour with a drop a FeCl3 . ii) Aqueous phenol gives white precipitate with bromine water. iii) Phenol gives blue colour with ammonia and sodium hypochlorite.

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